Exciton Annihilation Rate Research Articles

Excitonic origin of the optical properties of CsPbBr3

The optical properties of CsPbBr3 are studied with temperature dependent spectroscopic techniques. The samples are obtained from a method that has 10 % Pb waste compared with conventional ones. The dependence with temperature between 30 K and room temperature of the optical transmittance and photoluminescence is measured. Near bandgap optical properties are governed by structures originated in free excitons. Using the Elliott model for excitonic absorption, the dependence with temperature of bandgap energy and exciton binding energy are obtained. Both increase with temperature increase. Also, the width of the excitonic absorption and the inter-band absorption, which is assimilated to Urbach energy, were studied. Several models are used to extract parameters from these data. The excitonic absorption width follows the Segall model giving an exciton optical phonon interaction as the dominant term at room temperature. From several fittings, an effective optical phonon energy between 23 and 32 meV is obtained. The Urbach energy at 30 K reaches 10 meV which is related to a good crystalline quality of the samples. Several experimental results show that the origin of the photoluminescence is produced by direct recombination of free excitons. The first one is the similarity of the temperature dependence of photoluminescence width with the one of excitonic absorption. The second one is based in the activation energies obtained from the dependence of the integrated photoluminescence with temperature, one of which coincides with Excitonic Biding Energy. The third one is related to the dependence of the Stokes Shift with temperature which corresponds to the Gurioli model of excitonic thermalization. The last one comes from the dependence of the time resolved photoluminescence. Using rate equations, a radiative and non-radiative monomolecular time constant between 32 and 50 ns and an exciton-exciton annihilation rate constant between 1.0 and 6.0 × 10−7 cm3/s are obtained.

Ligand field exciton annihilation in bulk CrCl3.

The layered van der Waals material CrCl3 exhibits very strongly bound ligand field excitons that control optoelectronic applications and are connected with magnetic ordering by virtue of their d-orbital origin. Time-resolved photoluminescence of these exciton populations at room temperature shows that their relaxation is dominated by exciton-exciton annihilation and that the spontaneous decay lifetime is very long. These observations allow the rough quantification of the exciton annihilation rate constant and contextualization in light of a recent theory of universal scaling behavior of the annihilation process.

Control of Hybrid Exciton Lifetime in MoSe2/WS2 Moiré Heterostructures.

Hybrid excitons, characterized by their strong oscillation strength and long lifetimes, hold great potential as information carriers in semiconductors. They offer promising applications in exciton-based devices and circuits. MoSe2/WS2 heterostructures represent an ideal platform for studying hybrid excitons, but how to regulate the exciton lifetime has not yet been explored. In this study, layer hybridization is modulated by applying electric fields parallel or antiparallel to the dipole moment, enabling us to regulate the exciton lifetime from 1.36 to 4.60ns. Furthermore, the time-resolved photoluminescence decay traces are measured at different excitation power. A hybrid exciton annihilation rate of 8.9 × 10-4cm2s-1 is obtained by fitting. This work reveals the effects of electric fields and excitation power on the lifetime of hybrid excitons in MoSe2/WS2 1.5° moiré heterostructures, which play important roles in high photoluminescence quantum yield optoelectronic devices based on transition-metal dichalcogenides heterostructures.

Observation of enhanced WSe2 exciton–exciton annihilation in WSe2/Gr/hBN heterostructure

Due to strong quantum confinement effects and novel physical properties, two-dimensional transition metal dichalcogenides (TMDCs) as well as their heterostructures provide an attractive platform for studying excitonic effects and many-body interactions. However, manipulation on the excitonic effect in TMDCs remains challenge owing to the complex interplay of various factors. In this Letter, we report large exciton peak redshift and enhanced exciton–exciton annihilation in WSe2/Gr/hBN heterostructures investigated with static and transient optical spectroscopy. The pronounced redshift of exciton energy in the triple layer heterostructure arises from the charge transfer effect between graphene and WSe2, which leads to the reduction of the WSe2 exciton binding energy significantly due to the Coulomb screening effect. As a result, the reduced exciton binding energy increases the exciton delocalization in the WSe2 layer, leading to an increased probability of exciton–exciton collisions, which results in fast exciton annihilation rate. This study demonstrates the impact of graphene layer on exciton energy as well as the relaxation dynamics in WSe2/Gr/hBN heterostructures, which provides insights into the understanding of quasiparticle physics and many-body interactions in 2D materials.

Monolayer-like Exciton Recombination Dynamics of Multilayer MoSe2 Observed by Pump-Probe Microscopy.

Transition metal dichalcogenides (TMDCs) have garnered considerable interest over the past decade as a class of semiconducting layered materials. Most studies on the carrier dynamics in these materials have focused on the monolayer due to its direct bandgap, strong photoluminescence, and strongly bound excitons. However, a comparative understanding of the carrier dynamics in multilayer (e.g., >10 layers) flakes is still absent. Recent computational studies have suggested that excitons in bulk TMDCs are confined to individual layers, leading to room-temperature stable exciton populations. Using this new context, we explore the carrier dynamics in MoSe2 flakes that are between ∼16 and ∼125 layers thick. We assign the kinetics to exciton-exciton annihilation (EEA) and Shockley-Read-Hall recombination of free carriers. Interestingly, the average observed EEA rate constant (0.003 cm2/s) is nearly independent of flake thickness and 2 orders of magnitude smaller than that of an unencapsulated monolayer (0.33 cm2/s) but very similar to values observed in encapsulated monolayers. Thus, we posit that strong intralayer interactions minimize the effect of layer thickness on recombination dynamics, causing the multilayer to behave like the monolayer and exhibit an apparent EEA rate intrinsic to MoSe2.

Synergetic Enhancement of Quantum Yield and Exciton Lifetime of Monolayer WS2 by Proximal Metal Plate and Negative Electric Bias.

The efficiency of light emission is a critical performance factor for monolayer transition metal dichalcogenides (1L-TMDs) for photonic applications. While various methods have been studied to compensate for lattice defects to improve the quantum yield (QY) of 1L-TMDs, exciton-exciton annihilation (EEA) is still a major nonradiative decay channel for excitons at high exciton densities. Here, we demonstrate that the combined use of a proximal Au plate and a negative electric gate bias (NEGB) for 1L-WS2 provides a dramatic enhancement of the exciton lifetime at high exciton densities with the corresponding QY enhanced by 30 times and the EEA rate constant decreased by 80 times. The suppression of EEA by NEGB is attributed to the reduction of the defect-assisted EEA process, which we also explain with our theoretical model. Our results provide a synergetic solution to cope with EEA to realize high-intensity 2D light emitters using TMDs.

Exciton annihilation in molecular aggregates suppressed through quantum interference.

Exciton-exciton annihilation (EEA), an important loss channel in optoelectronic devices and photosynthetic complexes, has conventionally been assumed to be an incoherent, diffusion-limited process. Here we challenge this assumption by experimentally demonstrating the ability to control EEA in molecular aggregates using the quantum phase relationships of excitons. We employed time-resolved photoluminescence microscopy to independently determine exciton diffusion constants and annihilation rates in two substituted perylene diimide aggregates featuring contrasting excitonic phase envelopes. Low-temperature EEA rates were found to differ by more than two orders of magnitude for the two compounds, despite comparable diffusion constants. Simulated rates based on a microscopic theory, in excellent agreement with experiments, rationalize this EEA behaviour based on quantum interference arising from the presence or absence of spatial phase oscillations of delocalized excitons. These results offer an approach for designing molecular materials using quantum interference where low annihilation can coexist with high exciton concentrations and mobilities.

Ultrafast Spontaneous Localization of a Jahn-Teller Exciton Polaron in Two-Dimensional Semiconducting CrI3 by Symmetry Breaking.

The excited state species and properties in low-dimensional semiconductors can be completely redefined by electron-lattice coupling or a polaronic effect. Here, by combining ultrafast broadband pump-probe spectroscopy and first-principles GW and Bethe-Salpeter equation calculations, we show semiconducting CrI3 as a prototypical 2D polaronic system with characteristic Jahn-Teller exciton polaron induced by symmetry breaking. A photogenerated electron and hole in CrI3 localize spontaneously in ∼0.9 ps and pair geminately to a Jahn-Teller exciton polaron with elongated Cr-I octahedra, large binding energy, and an unprecedentedly small exciton-exciton annihilation rate constant (∼10-20 cm3 s-1). Coherent phonon dynamics indicates the localization is mainly triggered by the coherent nuclear vibration of the I-Cr-I out-of-plane stretch mode at 128.5 ± 0.1 cm-1. The excited state Jahn-Teller exciton polaron in CrI3 broadens the realm of 2D polaron systems and reveals the decisive role of coupled electron-lattice motion on excited state properties and exciton physics in 2D semiconductors.

Nonlinear optical absorption and ultrafast carrier's dynamics of ZrTe2 by Transient Absorption (TA) Spectrometer

The TMDCs (transition metal di-chalcogenides) family provides a platform to discover novel physical phenomena and exotic electronic properties for various device applications. The ultrafast carrier dynamics of the ZrTe2 sample demonstrate that Transient absorption (TA) signals have (electron-hole) constituents and trap carriers. TA variations depend upon carrier properties and photo-excitation due to spatially localized excitations. In the broadband positive signal obtain from ESA (Excited-State Absorption) and the negative signal from GSA (Ground State Absorption). It is seen that ESA is greater as compared to GSA due to fluence-dependent nonlinear absorption (NLA). To study the TA excitons dynamics of ZrTe2, we attribute positive probe bleach (PB) as hot excitons that are situated at higher excitonic states. The TA from power-dependent decay demonstrates that both types of excitons self-trapped excitons (STE) and free excitons (FE) have three processes, relaxation of ST excitons from F excitons, annihilation process between exciton-exciton and relaxation of the ground state from ST excitons states. The variation in exciton annihilation rate gives the exact information about exciton dynamics, which is the key aspect of transient absorption spectroscopy. The free charge carriers are largely localized and move faster compared to the non-localized trapped charge carriers.

Engineering Exciton Recombination Pathways in Bilayer WSe2 for Bright Luminescence.

Exciton-exciton annihilation (EEA) in counterdoped monolayer transition metal dichalcogenides (TMDCs) can be suppressed by favorably changing the band structure with strain. The photoluminescence (PL) quantum yield (QY) monotonically approaches unity with strain at all generation rates. In contrast, here in bilayers (2L) of tungsten diselenide (WSe2) we observe a nonmonotonic change in EEA rate at high generation rates accompanied by a drastic enhancement in their PL QY at low generation rates. EEA is suppressed at both 0% and 1% strain, but activated at intermediate strains. We explain our observation through the indirect to direct transition in 2L WSe2 under uniaxial tensile strain. By strain and electrostatic counterdoping, we attain ∼50% PL QY at all generation rates in 2L WSe2, originally an indirect semiconductor. We demonstrate transient electroluminescence from 2L WSe2 with ∼1.5% internal quantum efficiency for a broad range of carrier densities by applying strain, which is ∼50 times higher than without strain. The present results elucidate the complete optoelectronic photophysics where indirect and direct excitons are simultaneously present and expedite exciton engineering in a TMDC multilayer beyond indirect-direct bandgap transition.

Twist-angle-controlled neutral exciton annihilation in WS2 homostructures.

Exciton-exciton annihilation (EEA), as typical nonradiative recombination, plays an unpopular role in semiconductors. The nonradiative process significantly reduces the quantum yield of photoluminescence, which substantially inhibits the maximum efficiency of optoelectronic devices. Recently, laser irradiation, introducing defects and applying strain have become effective means to restrain EEA in two-dimensional (2D) transition metal dichalcogenides (TMDCs). However, these methods destroy the atomic structure of 2D materials and limit their practical applications. Fortunately, twisted structures are expected to validly suppress EEA through excellent interface quality. Here, we develop a non-destructive way to control EEA in WS2 homostructures by changing the interlayer twist angle, and systematically study the effect of interlayer twist angle on EEA, using fluorescence lifetime imaging measurement (FLIM) technology. Due to the large moiré potential at a small interlayer twist angle, the diffusion of excitons is hindered, and the EEA rate decreases from 1.01 × 10-1 cm2 s-1 in a 9° twisted WS2 homostructure to 4.26 × 10-2 cm2 s-1 in a 1° twisted WS2 homostructure. The results reveal the important role of the interlayer twist angle and EEA interaction in high photoluminescence quantum yield optoelectronic devices based on TMDC homostructures.

Dark exciton-exciton annihilation in monolayer WSe2

The exceptionally strong Coulomb interaction in semiconducting transition-metal dichalcogenides (TMDs) gives rise to a rich exciton landscape consisting of bright and dark exciton states. At elevated densities, excitons can interact through exciton-exciton annihilation (EEA), an Auger-like recombination process limiting the efficiency of optoelectronic applications. Although EEA is a well-known and particularly important process in atomically thin semiconductors determining exciton lifetimes and affecting transport at elevated densities, its microscopic origin has remained elusive. In this joint theory-experiment study combining microscopic and material-specific theory with time- and temperature-resolved photoluminescence measurements, we demonstrate the key role of dark intervalley states that are found to dominate the EEA rate in monolayer WSe$_2$. We reveal an intriguing, characteristic temperature dependence of Auger scattering in this class of materials with an excellent agreement between theory and experiment. Our study provides microscopic insights into the efficiency of technologically relevant Auger scattering channels within the remarkable exciton landscape of atomically thin semiconductors.

Universal Inverse Scaling of Exciton-Exciton Annihilation Coefficient with Exciton Lifetime.

Be it for essential everyday applications such as bright light-emitting devices or to achieve Bose-Einstein condensation, materials in which high densities of excitons recombine radiatively are crucially important. However, in all excitonic materials, exciton-exciton annihilation (EEA) becomes the dominant loss mechanism at high densities. Typically, a macroscopic parameter named EEA coefficient (CEEA) is used to compare EEA rates between materials at the same density; higher CEEA implies higher EEA rate. Here, we find that the reported values of CEEA for 140 different materials is inversely related to the single-exciton lifetime. Since during EEA one exciton must relax to ground state, CEEA is proportional to the single-exciton recombination rate. This leads to the counterintuitive observation that the exciton density at which EEA starts to dominate is higher in a material with larger CEEA. These results broaden our understanding of EEA across different material systems and provide a vantage point for future excitonic materials and devices.

Perceptible exciton-to-trion conversion and signature of defect mediated vibronic modes and spin relaxation in nanoscale WS2 exposed to γ-rays

In this work, we report manifested optical, optoelectronic and spin–spin relaxation features of a few layered tungsten disulphide (WS2) nanosheets subjected to energetic γ-photons (∼1.3 MeV) emitted from a Co60 source. Upon intense irradiation (dose = 96 kGy), a slight departure from the pure hexagonal phase was realized with the introduction of the trigonal phase at large. Moreover, in the Raman spectra, as a consequence of the radiation-induced effect, an apparent improvement of the E-to-A mode intensity and a reduction in phonon lifetimes have been realized, with the latter being dependent on the linewidths. The emergence of the new peak (D) maxima observable at ∼406 cm−1 in the Raman spectra and ∼680 nm in the photoluminescence (PL) spectra can be attributed to the introduction of defect centres owing to realization of sulphur vacancies (V S) in the irradiated nanoscale WS2. Additionally, neutral exciton to charged exciton (trion) conversion is anticipated in the overall PL characteristics. The PL decay dynamics, while following bi-exponential trends, have revealed ample improvement in both the fast parameter (0.39 ± 0.01 ns to 1.88 ± 0.03 ns) and the slow parameter (2.36 ± 0.03 ns to 12.1 ± 0.4 ns) after γ-impact. We attribute this to the finite band gap expansion and the incorporation of new localized states within the gap, respectively. A declining exciton annihilation rate is also witnessed. The isotropic nature of the electron paramagnetic resonance spectra as a consequence of γ-exposure would essentially characterize a uniform distribution of the paramagnetic species in the system, while predicting a three-fold improvement of relative spin density at 96 kGy. Exploring defect dynamics and spin dynamics in 2D nanoscale systems does not only strengthen fundamental insight but can also offer ample scope for designing suitable components in the areas of miniaturized optoelectronic and spintronic devices.

Long-range exciton transport and slow annihilation in two-dimensional hybrid perovskites

Two-dimensional hybrid organic-inorganic perovskites with strongly bound excitons and tunable structures are desirable for optoelectronic applications. Exciton transport and annihilation are two key processes in determining device efficiencies; however, a thorough understanding of these processes is hindered by that annihilation rates are often convoluted with exciton diffusion constants. Here we employ transient absorption microscopy to disentangle quantum-well-thickness-dependent exciton diffusion and annihilation in two-dimensional perovskites, unraveling the key role of electron-hole interactions and dielectric screening. The exciton diffusion constant is found to increase with quantum-well thickness, ranging from 0.06 ± 0.03 to 0.34 ± 0.03 cm2 s−1, which leads to long-range exciton diffusion over hundreds of nanometers. The exciton annihilation rates are more than one order of magnitude lower than those found in the monolayers of transition metal dichalcogenides. The combination of long-range exciton transport and slow annihilation highlights the unique attributes of two-dimensional perovskites as an exciting class of optoelectronic materials.

Carrier recombination mechanism in CsPbBr3 revealed by time-resolved photoluminescence spectroscopy

We systematically investigate the recombination mechanism of photogenerated charge carriers in bulk $\mathrm{CsPbB}{\mathrm{r}}_{3}$ by means of time-resolved photoluminescence (TR-PL) spectroscopy at low temperature and various laser excitation powers. A dynamic recombination model is proposed to describe the TR-PL that predicts the time-dependent exciton and free-charge populations. It provides a clear representation of competing mono- and bimolecular recombination processes. A decrease in carrier lifetime with increasing laser intensity was observed that was attributed to exciton-exciton scattering. A bimolecular recombination coefficient of $\ensuremath{\sim}{10}^{\ensuremath{-}7}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{3}/\mathrm{s}$ was obtained for exciton recombination. As the concentration of photoexcited carriers increases, stronger exciton-exciton annihilation occurs. The exciton-exciton annihilation rate for $\mathrm{CsPbB}{\mathrm{r}}_{3}$ is $3.63\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}7}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{3}\phantom{\rule{0.16em}{0ex}}{\mathrm{s}}^{\ensuremath{-}1}$ at 10-mW laser power. Notably, the exciton-exciton annihilation rate in bulk material is comparable to that obtained for photoexcited $\mathrm{CsPbB}{\mathrm{r}}_{3}$ nanoscale quantum dots.

Exciton-exciton annihilation in hBN

Known as a prominent recombination path at high excitation densities, exciton-exciton annihilation (EEA) is evidenced in bulk hexagonal boron nitride by cathodoluminescence at low temperature. Thanks to a careful tuning of the exciton density by varying either the current or the focus of the incident electron beam, we could estimate an EEA rate of 2 × 10−6 cm3 s−1 at T = 10 K, the highest reported so far for a bulk semiconductor. Expected to be even stronger in nanotubes or atomic layers, EEA probably contributes to the luminescence quenching observed in low-dimensionality BN materials.

Impeding Exciton–Exciton Annihilation in Monolayer WS2 by Laser Irradiation

Monolayer (1L) transition metal dichalcogenides (TMDs) are two-dimensional direct-bandgap semiconductors with promising applications of quantum light emitters. Recent studies have shown that intrinsically low quantum yields (QYs) of 1L-TMDs can be greatly improved by chemical treatments. However, nonradiative exciton–exciton annihilation (EEA) appears to significantly limit light emission of 1L-TMDs at a nominal density of photoexcited excitons due to strong Coulomb interaction. Here we show that the EEA rate constant (γ) can be reduced by laser irradiation treatment in mechanically exfoliated monolayer tungsten disulfide (1L-WS2), causing significantly improved light emission at the saturating optical pumping level. Time-resolved photoluminescence (PL) measurements showed that γ reduced from 0.66 ± 0.15 cm2/s to 0.20 ± 0.05 cm2/s simply using our laser irradiation. The laser-irradiated region exhibited lower PL response at low excitation levels, however at the high excitation level displayed 3× higher PL...

Suppression of exciton-exciton annihilation in tungsten disulfide monolayers encapsulated by hexagonal boron nitrides

We investigates exciton-exciton annihilation (EEA) in tungsten disulfide $(\mathrm{W}{\mathrm{S}}_{2})$ monolayers encapsulated by hexagonal boron nitride (hBN). It is revealed that decay signals observed by time-resolved photoluminescence (PL) are not strongly dependent on the exciton densities of hBN-encapsulated $\mathrm{W}{\mathrm{S}}_{2}$ monolayers $(\mathrm{W}{\mathrm{S}}_{2}/\mathrm{hBN})$. In contrast, the sample without the bottom hBN layer $(\mathrm{W}{\mathrm{S}}_{2}/\mathrm{Si}{\mathrm{O}}_{2})$ exhibits a drastic decrease of decay time with increasing exciton density due to the appearance of a rapid PL decay component, signifying nonradiative EEA-mediated recombination. Furthermore, the EEA rate constant of $\mathrm{W}{\mathrm{S}}_{2}/\mathrm{hBN}$ was determined as $(6.3\ifmmode\pm\else\textpm\fi{}1.7)\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}3}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{2}\phantom{\rule{0.16em}{0ex}}{\mathrm{s}}^{\ensuremath{-}1}$, being about 2 orders of magnitude smaller than that of $\mathrm{W}{\mathrm{S}}_{2}/\mathrm{Si}{\mathrm{O}}_{2}$. Thus, the observed EEA rate reduction played a key role in enhancing luminescence intensity at high exciton densities in the $\mathrm{W}{\mathrm{S}}_{2}$ monolayer.

Highly Efficient Full-Color Thermally Activated Delayed Fluorescent Organic Light-Emitting Diodes: Extremely Low Efficiency Roll-Off Utilizing a Host with Small Singlet-Triplet Splitting.

Numerous efforts have been devoted to boost the efficiency of thermally activated delayed fluorescence (TADF) devices; however, strategies to suppress the device efficiency roll-off are still in urgent need. Here, a general and effective approach to suppress the efficiency roll-off of TADF devices is proposed, that is, utilizing TADF materials as the hosts for TADF emitters. Bearing small singlet-triplet splitting (ΔEST) with donor and acceptor units, TADF materials as the hosts possess the potential to achieve matched frontier energy levels with the adjacent transporting layers, facilitating balanced charge injection as well as bipolar charge transport mobilities beneficial to the balanced charges transportation. Furthermore, an enhanced Förster energy transfer from the host to the dopant can be anticipated, helpful to reduce the exciton concentration. Based on the principles, a new TADF material based on indeno[2,1-b]carbazole/1,3,5-triazin derivation is synthesized and used as the universal host for the full-color TADF devices. Remarkable low efficiency roll-off was achieved with above 90% of the maximum external quantum efficiencies (EQEmax's) maintained even at a brightness of 2000 cd/m2, along with EQEmax's of 23.2, 21.0, and 19.2% for orange, green, and sky-blue TADF devices, respectively. Through computational simulation, we identified the suppressed exciton annihilation rates compared with devices adopting conventional hosts. The state-of-the-art low efficiency roll-off of those TADF devices manifests the great potential of such host design strategy, paving an efficient strategy toward their practical application.